EP3581609B1 - Acrylic resin biaxially stretched film and method for manufacturing the same - Google Patents

Acrylic resin biaxially stretched film and method for manufacturing the same Download PDF

Info

Publication number
EP3581609B1
EP3581609B1 EP18751700.8A EP18751700A EP3581609B1 EP 3581609 B1 EP3581609 B1 EP 3581609B1 EP 18751700 A EP18751700 A EP 18751700A EP 3581609 B1 EP3581609 B1 EP 3581609B1
Authority
EP
European Patent Office
Prior art keywords
acrylic resin
mass
film
group
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP18751700.8A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3581609A1 (en
EP3581609A4 (en
Inventor
Yuuki TAKASUKA
Naoto Fukuhara
Atsuhiro Nakahara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Publication of EP3581609A1 publication Critical patent/EP3581609A1/en
Publication of EP3581609A4 publication Critical patent/EP3581609A4/en
Application granted granted Critical
Publication of EP3581609B1 publication Critical patent/EP3581609B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the present invention relates to an acrylic resin biaxially stretched film and a method for manufacturing the same.
  • the present invention further relates to a polarizer protective film, a decorative film, and a layered film that use the acrylic resin biaxially stretched film.
  • a (meth)acrylic resin (which is referred to as a PMMA resin in some cases below) has high transparency, and is suitable for use as an optical member, an illuminating member, a signboard member, and a decorative member.
  • a film made from a (meth)acrylic resin composition as a material has been used for applications, for example, a polarizer protective film, a decorative film, and the like.
  • Patent Literature 1 discloses a method for manufacturing a resin composition having transparency and impact resistance by blending a polycarbonate resin (which is referred to as a PC resin in some cases below) with the PMMA.
  • Patent Literature 2 discloses a resin composition for an optical material in which 2 to 10 parts by weight of a PC resin are blended as a phase difference correcting agent for use as an optical member.
  • Patent Document 3 discloses a method for manufacturing a transparent film by stretching a resin composition containing a (meth)acrylic resin, or a (meth)acrylic resin and a polycarbonate resin.
  • Patent Literature 1 discloses a method for manufacturing a transparent resin composition
  • Patent Literature 2 discloses a resin composition for an optical material having a low phase difference, they make no mention of processing conditions of the resin composition and control of physical properties of a film according to the conditions.
  • the stretched film of a resin composition containing a (meth)acrylic resin composition and a polycarbonate resin that Patent Document 3 discloses has a large linear expansion coefficient and insufficient impact resistance.
  • Patent Literature 4 describes a film and process for producing the same.
  • Patent Literature 5 discloses a methacrylic resin composition and molded body.
  • Patent Literature 6 describes a biaxially stretched film and method for manufacturing same, polarizer protective film, decorative film, and layered film.
  • the present invention has been made in view of the problems of the aforementioned related techniques and an object thereof is to solve the problems explained hereinafter.
  • the present invention provides an acrylic resin film having a low linear expansion property, an excellent impact resistance, a high shrinkage starting temperature and an excellent dimensional stability. Further, the present invention provides a method for manufacturing a stretching film having a high shrinkage starting temperature and an excellent dimensional stability.
  • the acrylic resin biaxially stretched film according to the present invention has a high light transmittance, a low haze, a small linear expansion coefficient, a high shrinkage starting temperature, an excellent impact resistance, so that it is suitable for optical members and automobile members.
  • the acrylic resin biaxially stretched film according to the present invention is an acrylic resin film containing 99.9 to 50 mass% of a (meth)acrylic resin [A] having a glass transition temperature T A of 140°C or lower, and 0.1 to 50 mass% of a thermoplastic resin [B] having a glass transition temperature T B of (T A +10°C) or higher, in which a shrinkage starting temperature is 110°C or higher, a linear expansion coefficient is 60 ppm/°C or less, and an impact resistance strength is 4.5 J/mm or more.
  • a (meth)acrylic resin [A] having a glass transition temperature T A of 140°C or lower
  • a thermoplastic resin [B] having a glass transition temperature T B of (T A +10°C) or higher in which a shrinkage starting temperature is 110°C or higher, a linear expansion coefficient is 60 ppm/°C or less, and an impact resistance strength is 4.5 J/mm or more.
  • the "glass transition temperature” herein is an intermediate glass transition temperature obtained from a DSC curve that is measured under the condition where the temperature is raised by using a differential scanning calorimetry in accordance with JIS K7121.
  • the glass transition temperature can be measured by the methods described in the [Example].
  • the (meth)acrylic resin (A) is not limited to particular resins and any (meth)acrylic polymer and a mixture thereof having the glass transition temperature T A of 140°C or lower may be used.
  • the (meth)acrylic resin (A) contains one or more types of methacrylate ester monomer units such as a methyl methacrylate (MMA) monomer unit.
  • MMA methyl methacrylate
  • methacrylate ester examples include: methacrylic acid alkyl esters such as MMA, ethyl methacrylate and butyl methacrylate; methacrylic acid aryl esters such as phenyl methacrylate; methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate and norbornenyl methacrylate. Among them, a methacrylic acid alkyl ester is preferred, and MMA is most preferred.
  • the content of the methacrylate ester monomer unit in the (meth)acrylic resin (A) is preferably 20 mass% or more, more preferably 50 mass% or more.
  • Examples of the (meth)acrylic resin (A) include a methacrylic copolymer (A1) containing a methacrylate ester monomer as a primary component, and a methacrylic copolymer (A2) containing a methacrylate ester monomer unit and a structural unit having a ring structure in the main chain.
  • the (meth)acrylic resin (A) is not limited to resins composed of only one type of the above-mentioned polymers, and may contain a plurality of methacrylic copolymers as long as it is a combination capable of achieving compatibility.
  • the content of the methacrylate ester monomer unit in the methacrylic copolymer (A1) is preferably 90 mass% or more, more preferably 95 mass% or more, even more preferably 98 mass% or more, particularly preferably 99 mass% or more, and most preferably 100 mass%.
  • the content of the MMA monomer unit in the methacrylic copolymer (A1) is preferably 90 mass% or more, more preferably 95 mass% or more, even more preferably 98 mass% or more, particularly preferably 99 mass% or more, and most preferably 100 mass%.
  • the methacrylic copolymer (A1) may contain one or more types of monomer units other than the methacrylate ester monomer unit.
  • monomer units include structural units derived from vinyl monomers containing only one polymerizable carbon-carbon double bond in one molecule, for example, acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; an acrylic acid aryl ester such as phenyl acrylate; acrylic acid cycloalkyl esters such as cyclohexyl acrylate and norbornenyl acrylate; aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; acrylamide and methacrylamide; and nitriles such as acrylonitrile and methacrylonitrile.
  • An Mw of the methacrylic copolymer (A1) is preferably 40,000 to 200,000, more preferably 50,000 to 150,000, and particularly preferably 80,000 to 120,000. With the Mw of 40,000 or more, the mechanical strength (impact resistance and toughness, etc.) of the resultant molded article is likely to increase, and with the Mw of 200,000 or less, the fluidity of the (meth)acrylic resin composition is likely to increase, thereby increasing the formability thereof.
  • a molecular weight distribution (Mw/Mn) of the methacrylic copolymer (A1) is preferably 1.6 to 5.0, more preferably 1.7 to 3.0, and particularly preferably 1.7 to 2.0.
  • Mw/Mn molecular weight distribution within such a range
  • An Mw and an Mw/Mn can be controlled by adjusting the type and/or the amount of a polymerization initiator used at the time of manufacturing the methacrylic copolymer (A1).
  • a melt flow rate (MFR) of the methacrylic copolymer (A1) measured at 230°C and 3.8 kg load is preferably 0.1 g/10 min or more, more preferably 0.1 to 30 g/10 min, even more preferably 0.2 to 15 g/10 min, particularly preferably 0.5 to 10 g/ 10 min, and most preferably 1.0 to 3.0 g/10 min.
  • the methacrylic copolymer (A1) can be manufactured by using known polymerization methods such as a radical polymerization method and an anionic polymerization method.
  • a radical polymerization method it is possible to select a known polymerization method, for example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method to manufacture the methacrylic copolymer while as the anionic polymerization method, it is possible to select a known polymerization method, for example, a bulk polymerization method and a solution polymerization method to manufacture the methacrylic copolymer.
  • the radical polymerization method it is possible to perform the radical polymerization method in the absence of solvent or in a solvent. In order to obtain the methacrylic copolymer (A1) having a low impurity concentration, it is preferred that the radical polymerization method be performed in the absence of solvent.
  • the polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen gas at a low dissolved oxygen level in order to prevent the molded article from silvering or coloring.
  • Examples of a polymerization initiator used in the radical polymerization method include: t-hexylperoxyisopropyl monocarbonate; t-hexylperoxy 2-ethylhexanoate; 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate; t-butylperoxypivalate; t-hexylperoxypivalate; t-butylperoxyneodecanoate; t-hexylperoxyneodecanoate; 1,1,3,3-tetramethylbutylperoxyneodecanoate; 1,1-bis(t-hexylperoxy)cyclohexane; benzoyl peroxide; 3,5,5-trimethylhexanoylperoxide; lauroyl peroxide; 2,2'-azobis(2-methylpropionitrile); 2,2'-azobis(2-methylbutyronitrile), and dimethyl 2,2'-azobis(
  • t-hexylperoxy 2-ethylhexanoate 1,1-bis(t-hexylperoxy)cyclohexane, and dimethyl 2,2'-azobis(2-methylpropionate) are preferred.
  • One or more types of the polymerization initiators can be used.
  • the 1 hour half-life temperature of the polymerization initiator is preferably 60 to 140°C, more preferably 80 to 120°C.
  • the polymerization initiator preferably has a hydrogen abstraction ability of 20% or less, more preferably 10% or less, particularly preferably 5% or less.
  • the amount of the polymerization initiator used is, with respect to 100 parts by mass of one or more types of monomers used for a polymerization reaction, preferably 0.0001 to 0.02 parts by mass, more preferably 0.001 to 0.01 parts by mass, and particularly preferably 0.005 to 0.007 parts by mass.
  • the hydrogen abstracting ability can be measured by a radical trapping method ( ⁇ -methyl styrene dimer trapping method) using ⁇ -methyl styrene dimer. This measurement is commonly performed as follows. First, radical fragments are generated by cleaving the polymerization initiator with the presence of ⁇ -methylstyrene dimer as a radical trapping agent.
  • a radical fragment having a low hydrogen abstraction ability is bound to and trapped by a double bond of ⁇ -methylstyrene dimer.
  • a radical fragment having a high hydrogen abstraction ability extracts hydrogen from cyclohexane to generate a cyclohexyl radical, and this cyclohexyl radical is bound to and trapped by a double bond of ⁇ -methylstyrene dimer to form a cyclohexane trapped product.
  • a ratio (a mole fraction) of radical fragments having a high hydrogen abstraction ability with respect to the quantity of the theoretically generated radical fragments, which is obtained by determining the quantity of cyclohexane or a cyclohexane trapped product, is obtained as hydrogen abstraction ability.
  • Examples of a chain transfer agent used in the radical polymerization method include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropionate, butanediol bisthioglycolate, butanediol bisthiopropionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tris-( ⁇ -thiopropionate), and pentaerythritol tetrakisthiopropionate.
  • monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferred.
  • the amount of the chain transfer agent used is, with respect to 100 parts by mass of one or more types of monomers used for a polymerization reaction, preferably 0.01 to 1 part by mass, more preferably 0.05 to 0.8 parts by mass, particularly preferably 0.1 to 0.6 parts by mass, and most preferably 0.10 to 0.5 parts by mass.
  • the amount of the chain transfer agent used is, with respect to 100 parts by mass of the polymerization initiator, preferably 2,500 to 10,000 parts by mass, more preferably 3,000 to 9,000 parts by mass, and particularly preferably 3,500 to 6,000 parts by mass.
  • Solvents used in the radical polymerization method are preferably aromatic hydrocarbons such as benzene, toluene, and ethylbenzene.
  • aromatic hydrocarbons such as benzene, toluene, and ethylbenzene.
  • One or more types of solvents can be used.
  • the amount of the solvent used is preferably 100 parts by mass or less, and more preferably 90 parts by mass or less with respect to 100 parts by mass of the polymerization reaction raw material.
  • a polymerization reaction temperature is preferably 100 to 200°C and more preferably 110 to 180°C. With the polymerization temperature of 100°C or higher, productivity is likely to be improved due to improvement in polymerization rate and reduction in viscosity of the polymerization solution.
  • the polymerization temperature of 200°C or lower makes it possible to easily control the polymerization rate, to reduce further generation of by-products, and to reduce coloring of the resin.
  • the polymerization reaction time is preferably 0.5 to 4 hours, more preferably 1.5 to 3.5 hours, and particularly preferably 1.5 to 3 hours. Note that the polymerization reaction time when a continuous flow reactor is used is an average residence time in a reactor.
  • a polymerization conversion rate in the radical polymerization method is preferably 20 to 80 mass%, more preferably 30 to 70 mass%, and particularly preferably 35 to 65 mass%. With the polymerization conversion rate of 20 mass% or more, remaining unreacted monomers tend to be easily removed, thereby obtaining a molded article having a good appearance. With the polymerization conversion rate is 70 mass% or less, viscosity of the polymerization solution tends to be reduced, thereby increasing productivity.
  • a reactor may be either a batch type or a continuous flow type, and a continuous flow reactor is preferred in view of productivity.
  • the polymerization reaction raw material a mixed solution containing one or more monomers, a polymerization initiator and a chain transfer agent and so on
  • the prepared material is supplied to a reactor at a constant flow rate, and then liquid in the reactor is extracted at a flow rate corresponding to the supply amount.
  • a reactor include a tubular reactor which can be brought into a state close to a plug flow one or a tank reactor which can be brought into a state close to a completely mixed one.
  • One or more reactors may be used, and at least one continuous-flow tank reactor is preferably used.
  • the amount of the liquid in the tank reactor during the polymerization reaction is preferably 1/4 to 3/4 and more preferably 1/3 to 2/3 with respect to a volume of the tank reactor.
  • An agitating apparatus is usually attached to the reactor.
  • the agitating apparatus include a static agitating apparatus and a dynamic agitating apparatus.
  • the dynamic agitating apparatus include a Maxblend type agitating apparatus, an agitating apparatus having a grid-like wing rotating around a vertical rotating shaft provided at the center, a propeller type agitating apparatus, and a screw type agitating apparatus. Among them, a Maxblend type agitating apparatus is preferred in order to mix uniformly.
  • a heat devolatilization method is preferred as a removal method.
  • the devolatilization method include an equilibrium flash method and an adiabatic flash method.
  • the devolatilization temperature in the adiabatic flash method is preferably 200 to 280°C, and more preferably 220 to 260°C.
  • the heating time of a resin in the adiabatic flash method is preferably 0.3 to 5 minutes, more preferably 0.4 to 3 minutes, and particularly preferably 0.5 to 2 minutes.
  • a yellow index of the recovered monomers may be increased by heat applied during the recovery operation or the like. The yellow index is preferably reduced by purifying the recovered monomers by a known method.
  • Examples of a method for controlling a molecular weight distribution include a controlled polymerization method, and a living radical polymerization method and a living anionic polymerization are preferred.
  • Examples of the living radical polymerization method include an atom transfer radical polymerization (ATRP) method, a reversible addition fragmentation chain transfer (RAFT) polymerization method, a nitroxide-mediated polymerization (NMP) method, a boron-mediated polymerization method, and a catalyst chain transfer (CCT) polymerization method.
  • ATRP atom transfer radical polymerization
  • RAFT reversible addition fragmentation chain transfer
  • NMP nitroxide-mediated polymerization
  • CCT catalyst chain transfer
  • Examples of the (living) anionic polymerization method include: a method for performing an anionic polymerization in the presence of a mineral acid salt such as a salt of an alkali metal or an alkaline earth metal using an organic alkali metal compound as a polymerization initiator (see Japanese Examined Patent Publication No. H7-25859 ); a method for performing an anionic polymerization in the presence of an organoaluminum compound using an organic alkali metal compound as a polymerization initiator (see Japanese Unexamined Patent Publication No. H11-335432 ); and a method for performing an anionic polymerization using an organic rare earth metal complex as a polymerization initiator (see Japanese Unexamined Patent Publication No. H6-93060 ).
  • Lithium alkyls such as n-butylithium, sec-butylithium, isobutylithium, and tert-butylithium are preferred as a polymerization initiator used in the anionic polymerization method.
  • An organoaluminum compound preferably coexists in view of productivity.
  • organoaluminum compound examples include a compound represented by the expression: AlR A R B R C (in the expression, R A to R C each independently indicates, an alkyl group which has no substituent or which has a substituent, a cycloalkyl group which has no substituent or which has a substituent, an aryl group which has no substituent or which has a substituent, an aralkyl group which has no substituent or which has a substituent, an alkoxyl group which has no substituent or which has a substituent, an aryloxy group which has no substituent or which has a substituent or an N, N-disubstituted amino group.
  • R B and R C may be an arylenedioxy group which has no substituent or which has a substituent, in combination.).
  • organoaluminum compound examples include isobutylbis(2,6-di-tert-butyl-4-methylphenoxy)aluminum, isobutylbis(2,6-di-tert-butylphenoxy)aluminum, and isobutyl[2,2'-methylenebis(4-methyl-6-tert-butylphenoxy) aluminum.
  • ether In the anion polymerization method, ether, a nitrogen-containing compound and the like may coexist in order to control polymerization reaction.
  • a structural unit having a ring structure in the main chain in a methacrylic copolymer (A2) a structural unit containing a lactone ring unit, a maleic anhydride unit, a glutaric anhydride unit, a glutarimide unit, an N-substituted maleimide unit, or a tetrahydropyran ring unit are preferred as the ring structure.
  • Examples of a method for manufacturing the methacrylic copolymer (A2) include: a method for copolymerizing a cyclic monomer having polymerizable unsaturated carbon-carbon double bonds such as maleic anhydride and N-substituted maleimide with MMA or the like; and a method for intramolecularly cyclizing a part of the molecular chains of the methacrylic copolymer obtained by polymerization.
  • the content of the MMA monomer unit in the methacrylic copolymer (A2) is preferably 20 to 99 mass%, more preferably 30 to 95 mass%, and particularly preferably 40 to 90 mass%, and the content of the structural unit having a ring structure in the main chain is preferably 1 to 80 mass%, more preferably 5 to 70 mass%, and particularly preferably 10 to 60 mass%.
  • the content of the MMA monomer unit in the methacrylic copolymer (A2) does not include an MMA monomer unit which has been converted into a structural unit having a ring structure in the main chain by intramolecular cyclization among the MMA monomer units.
  • lactonediyl structural units such as ⁇ -propiolactonediyl (also known as oxooxetanediyl) structural unit, ⁇ -butyrolactonediyl (also known as 2-oxodihydrofurandiyl) structural unit, and ⁇ -valerolactonediyl (also known as 2-oxodihydropyranediyl) structural unit.
  • Examples of the ⁇ -valerolactonediyl structural unit include a structural unit expressed by the following formula (c).
  • R 4 and R 5 are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and it is preferred that R 4 be a hydrogen atom and R 5 be a methyl group.
  • R 6 is - COOR, and R is a hydrogen atom or an organic residue having 1 to 20 carbon atoms and is preferably a methyl group. "*" means a bond.
  • Examples of the aforementioned organic residue include a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, a -OAc group, and a -CN group.
  • the organic residue may contain an oxygen atom.
  • "Ac” represents an acetyl group.
  • the carbon number of the organic residue is preferably 1 to 10, and more preferably 1 to 5.
  • the (meth)acrylic resin can contain the ⁇ -valerolactonediyl structural unit, for example, by intramolecular cyclization of two MMA monomer units adjacent to each other.
  • Examples of the 2,5-dioxodihydrofurandiyl structural unit include a structural unit expressed by the following formula (d).
  • R 7 and R 8 are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms. "*" means a bond.
  • Examples of the aforementioned organic residue include a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, a -OAc group, and a -CN group.
  • the organic residue may contain an oxygen atom.
  • "Ac” represents an acetyl group.
  • the carbon number of the organic residue is preferably 1 to 10, and more preferably 1 to 5.
  • R 7 and R 8 both are preferably hydrogen atoms.
  • styrene and the like are preferably copolymerized in view of ease of manufacturing and an adjustment of intrinsic birefringence.
  • a copolymer having a styrene monomer unit, an MMA monomer unit and a maleic anhydride monomer unit disclosed in International Patent Publication No. WO2014/021264 and the like may be used.
  • the (meth)acrylic resin can contain the 2,5-dioxodihydrofurandiyl structural unit, for example, by copolymerization using maleic anhydride.
  • Examples of the 2,6-dioxodihydropyrandiyl structural unit include a structural unit expressed by the following formula (e).
  • R 9 and R 10 are each independently a hydrogen atom or an organic residue having 1 to 20 carbon atoms. "*" means a bond.
  • Examples of the aforementioned organic residue include a linear or branched alkyl group, a linear or branched alkylene group, an aryl group, a -OAc group, and a -CN group.
  • the organic residue may contain an oxygen atom.
  • "Ac” represents an acetyl group.
  • the organic residue preferably has a carbon number of 1 to 10, more preferably has a carbon number of 1 to 5, and is particularly preferably a methyl group.
  • the (meth)acrylic resin can contain the 2,6-dioxodihydropyrandiyl structural unit, for example, by intramolecular cyclization of two MMA monomer units adjacent to each other.
  • Examples of the 2,6-dioxopiperidinediyl structural unit include a structural unit expressed by the following formula (f).
  • R 11 and R 12 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 13 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • "*" means a bond.
  • R 11 and R 12 are preferably each independently a hydrogen atom or a methyl group, and it is more preferred that R 11 be a methyl group and R 12 be a hydrogen atom.
  • R 13 is preferably a hydrogen atom, a methyl group, an n-butyl group, a cyclohexyl group or a benzyl group, and more preferably a methyl group.
  • Examples of the 2,5-dioxopyrrolidinediyl structural unit include a structural unit expressed by the following formula (g).
  • R 15 and R 16 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 6 to 14 carbon atoms.
  • R 14 is an arylalkyl group having 7 to 14 carbon atoms, or an aryl group having 6 to 14 carbon atoms which has no substituent or which has a substituent.
  • the substituent here is a halogeno group, a hydroxyl group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an arylalkyl group having 7 to 14 carbon atoms.
  • "*" means a bond.
  • R 14 is preferably a phenyl group or a cyclohexyl group, and R 15 and R 16 are both preferably hydrogen atoms.
  • the (meth)acrylic resin can contain the 2,5-dioxopyrrolidinediyl structural unit, for example, by copolymerization using N-substituted maleimide.
  • Examples of the structural unit containing a >CH-O-CH ⁇ group in the ring structure include an oxetanediyl structural unit, a tetrahydrofurandiyl structural unit, a tetrahydropyrandiyl structural unit, and an oxepanediyl structural unit.
  • >C in the formula means that there are two bonds at a carbon atom C.
  • Examples of the tetrahydropyrandiyl structural unit include a structural unit expressed by the following formula (h).
  • R 17 and R 18 are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms having a ring structure. "*" means a bond. It is preferred that R 17 and R 18 be each independently a tricyclo [5.2.1.0 2,6 ] decanyl group, a 1,7,7-trimethylbicyclo [2.2.1] heptan-3-yl group, a t-butyl group, and a 4-t-butylcyclohexanyl group.
  • a ⁇ -valerolactonediyl structural unit and a 2,5-dioxodihydrofurandiyl structural unit are preferable in view of raw materials and ease of manufacturing.
  • a molecular weight distribution (a ratio Mw/Mn of a weight average molecular weight (Mw) to the number average molecular weight (Mn)) of the methacrylic copolymer (A2) is preferably 1.2 or greater and 5.0 or less, more preferably 1.3 or greater and 3.5 or less.
  • Mw/Mn a weight average molecular weight
  • Mn number average molecular weight
  • the Mw and Mn herein are values obtained by converting the chromatogram measured by gel permeation chromatography (GPC) into a molecular weight of standard polystyrene.
  • the Mw and the Mw/Mn can be measured by the methods described in the [Example] section.
  • the glass transition temperature of the methacrylic copolymer (A2) is preferably 120°C or higher, more preferably 123°C or higher, and particularly preferably 124°C or higher.
  • thermoplastic resin (B) is not limited to particular resins and any resins of which the glass transition temperature T B is, with respect to the glass transition temperature T A of the (meth)acrylic resin (A), at least (T A +10°C) may be used.
  • thermoplastic resin used for a thermoplastic resin layer include:
  • thermoplastic resins resins having high compatibility with the (meth)acrylic resin (A) are suitable in view of transparency.
  • a (meth)acrylic resin (B1) having a high triad syndiotacticity (rr), a polycarbonate resin (B2), a copolymer (B3) composed of at least a structural unit derived from an aromatic vinyl compound (a) and a structural unit derived from an acid anhydride (b), and the like may be used.
  • the (meth)acrylic resin (B1) has a triad syndiotacticity (rr) of 65% or more, preferably 70 to 90%, more preferably 72 to 85%, and even more preferably 74% to 80%.
  • the triad syndiotacticity (rr) of 65% or more significantly increases the glass transition temperature T B , thereby increasing heat resistance and impact resistance of the resultant stretching film.
  • a molecular weight distribution (Mw/Mn) of the (meth)acrylic resin (B1) is preferably 1.0 to 1.8, more preferably 1.0 to 1.4, even more preferably 1.02 to 1.3, and particularly preferably 1.03 to 1.1.
  • An Mw and an Mw/Mn can be controlled by adjusting the type and/or the amount of a polymerization initiator used at the time of manufacturing.
  • the (meth)acrylic resin (B1) may contain one or more types of monomer units other than the aforementioned MMA monomer unit.
  • monomer units include structural units derived from vinyl monomers containing only one polymerizable carbon-carbon double bond in one molecule, for example, acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; an acrylic acid aryl ester such as phenyl acrylate; acrylic acid cycloalkyl esters such as cyclohexyl acrylate and norbornenyl acrylate; aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; and nitriles such as acrylonitrile and methacrylonitrile.
  • An Mw of the (meth)acrylic resin (B1) is preferably 40,000 to 200,000, more preferably 40,000 to 150,000, even more preferably 50,000 to 120,000, and particularly preferably 50,000 to 90,000. With the Mw of 40,000 or more, the mechanical strength (impact resistance and toughness, etc.) of the resultant molded article is likely to increase, and with the Mw of 200,000 or less, the fluidity of the (meth)acrylic resin composition is likely to increase, thereby increasing the formability thereof.
  • a melt flow rate (MFR) of the (meth)acrylic resin (B1) measured at 230°C and 3.8 kg load is preferably 0.1 g/10 min or more, more preferably 0.2 to 30 g/10 min, even more preferably 0.5 to 20 g/10 min, particularly preferably 0.5 to 10 g/10 min, and most preferably 1.0 to 3.0 g/10 min.
  • a method for manufacturing the (meth)acrylic resin (B1) is as described above.
  • PC polycarbonate resin
  • An aromatic polycarbonate resin is preferably used in view of compatibility with the (meth)acrylic resin and transparency of the resultant molded article,
  • the polycarbonate resin (PC) preferably has a melt volume flow rate (MVR) measured at 300°C and 1.2 kg load of 15 to 250 cm 3 /10 min, more preferably 20 to 230 cm 3 /10 min, even more preferably 25 to 230 cm 3 /10 min, and particularly preferably 150 to 220 cm 3 /10 min.
  • MVR melt volume flow rate
  • the polycarbonate resin (PC) preferably has the polystyrene-equivalent Mw of 15,000 to 40,000, more preferably 18,000 to 39,000, even more preferably 20,000 to 38,000, and particularly preferably 20,000 to 25,000.
  • the MVR and the Mw of the polycarbonate resin (PC) can be controlled by adjusting the amount of a chain-terminating agent and/or a branching agent.
  • the glass transition temperature of the polycarbonate resin (PC) is preferably 130°C or higher, more preferably 135°C or higher, and particularly preferably 140°C or higher.
  • the upper limit of the glass transition temperature is usually 180°C.
  • the aromatic polycarbonate resin can be manufactured by performing processing of adjusting the amount of terminal hydroxy groups on the polycarbonate resin raw material manufactured by the melt polymerization method.
  • the polycarbonate resin (PC) may contain structural units such as polyester, polyurethane, polyether or polysiloxane other than the polycarbonate structural unit.
  • Suitable examples can include the SMA resin (B3) composed of at least a structural unit derived from an aromatic vinyl compound (a) expressed by the following general formula (a) and a structural unit derived from an acid anhydride (b) expressed by the following general formula (b).
  • SMA resin (B3) composed of at least a structural unit derived from an aromatic vinyl compound (a) expressed by the following general formula (a) and a structural unit derived from an acid anhydride (b) expressed by the following general formula (b).
  • R 1 and R 2 each independently indicates a hydrogen atom or an alkyl group.
  • R 3 and R 4 each independently indicates a hydrogen atom or an alkyl group.
  • an alkyl group having 12 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and a dodecyl group are preferred, and an alkyl group having 4 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group
  • a hydrogen atom, a methyl group, an ethyl group and a t-butyl group are preferred as R 1 .
  • a hydrogen atom, a methyl group, and an ethyl group are preferred as R 2 , R 3 , and R 4 .
  • the content of the structural unit derived from the aromatic vinyl compound (a) in the aforementioned SMA resin is preferably in the range of 50 to 85 mass%, more preferably in the range of 55 to 82 mass%, and even more preferably 60 to 80 mass%.
  • the resin composition (C) is excellent in moisture resistance and transparency.
  • aromatic vinyl compound (a) examples include: styrene; nuclear alkyl-substituted styrene such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, and 4-tert-butylstyrene; and ⁇ -alkyl substituted styrene such as ⁇ -methylstyrene, and 4-methyl- ⁇ -methylstyrene, and styrene is preferred in view of availability.
  • a single type of these aromatic vinyl compounds (a) may be used alone or a plurality of types of them may be used in combination.
  • the content of the structural unit derived from the acid anhydride (b) in the aforementioned SMA resin is preferably in the range of 15 to 50 mass%, more preferably in the range of 18 to 45 mass%, and even more preferably 20 to 40 mass%.
  • the resin composition (B3) has a high glass transition temperature and is excellent in mechanical strength.
  • Examples of the acid anhydride (b) include maleic anhydride, citraconic anhydride and dimethylmaleic anhydride, and maleic anhydride is preferred in view of availability.
  • a single type of these acid anhydrides (b) may be used alone or a plurality of types of them may be used in combination.
  • the aforementioned SMA resin may contain a structural unit derived from a methacrylic acid ester monomer in addition to the aromatic vinyl compound (a) and the acid anhydride (b).
  • methacrylate ester examples include: MMA; ethyl methacrylate; propyl methacrylate; isopropyl methacrylate; n-butyl methacrylate; isobutyl methacrylate; t-butyl methacrylate; 2-ethylhexyl methacrylate; cyclohexyl methacrylate; phenyl methacrylate; benzyl methacrylate; and 1-phenylethyl methacrylate.
  • methacrylic acid esters a methacrylic acid alkyl ester having 1 to 7 carbon atoms in the alkyl group is preferred, and MMA is particularly preferred because the SMA resin having an excellent heat resistance and transparency can be obtained. Further, a single type the methacrylic acid ester many be used alone or a plurality of types of the methacrylic acid esters may be used in combination.
  • the SMA resin may have a structural unit derived from monomers other than the aromatic vinyl compound (a), the acid anhydride (b) and the methacrylic acid ester.
  • examples of such other monomers include acrylic esters such as MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pen
  • a single type of these other monomers may be used alone or a plurality of types of them may be used in combination.
  • the content of the structural unit derived from such other monomers in the SMA resin is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 2 mass% or less.
  • the aforementioned SMA resin is obtained by polymerizing the aforementioned aromatic vinyl compound (a), acid anhydride (b), methacrylate ester and other monomers which are optional components.
  • the monomers to be used are mixed to prepare a monomer mixture, and the prepared monomer mixture is used for such polymerization.
  • Polymerization is not limited to particular methods, but in view of productivity, radical polymerization is preferably performed by methods such as a bulk polymerization method and a solution polymerization method.
  • the Mw of the aforementioned SMA resin is preferably in the range of 40,000 to 300,000. It is more preferably in the range of 100,000 to 200,000, and particularly preferably in the range of 150,000 to 180,000. With the Mw of 40,000 or more, a stretched film is excellent in heat resistance and impact resistance, and with the Mw of 300,000 or less, a raw film for stretching has an excellent molding processability, thereby increasing productivity of a laminate according to the present invention.
  • thermoplastic resin composition (C) is a resin composition composed of the aforementioned (meth)acrylic resin (A) and thermoplastic resin (B).
  • the content of the thermoplastic resin composition (B) is 0.1 mass% or more but less than 50 mass%, preferably 0.3 mass% or more but less than 20 mass%, more preferably 0.5 mass% or more but less than 5 mass%, and particularly preferably 0.7 mass% or more but less than 2 mass%.
  • the content of the thermoplastic resin (B) is 50 mass% or less, preferably 15 mass% or less, and more preferably 5 mass% or less.
  • a small amount of the thermoplastic resin (B) is preferably added in order to take advantage of features of the (meth)acrylic resin such as thermal stability and transparency. For example, if the thermoplastic resin composition (C), which contains the (meth)acrylic resin (A1) and the (meth)acrylic resin (B1), contains too large an amount of the (meth)acrylic resin (B1), the thermal stability thereof during heating is reduced.
  • the (meth)acrylic resin composition according to the present invention can contain one or more types of polymers other than the (meth)acrylic resin (A) and the thermoplastic resin (B) as necessary. Note that other polymers may be added during or after polymerization for the (meth)acrylic resin (A) and/or the thermoplastic resin (B), or may be added during kneading of the (meth)acrylic resin (A) and the thermoplastic resin (B).
  • polymers examples include: a phenoxy resin; polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; an ethylene ionomer; styrene resins such as polystyrene, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyamide resins such as nylon 6, nylon 66, and polyamide elastomer; polycarbonate; polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl phenol, and an ethylenevinyl alcohol copolymer; polyacetal; polyurethane; a modified polyphenylene ether and polyphenylene sulf
  • a phenoxy resin (PR) is a thermoplastic polyhydroxy polyether resin.
  • the phenoxy resin (PR) can contain 50 mass% or more of one or more types of structural units expressed by the following formula (i).
  • X is a divalent group containing at least one benzene ring
  • R is a linear or branched alkylene group having 1 to 6 carbon atoms.
  • the structural units expressed by the formula (i) may be connected at random, alternately, or in a block.
  • the number of the structural units expressed by the formula (i) contained in the phenoxy resin (PR) is preferably 10 to 1,000, more preferably 15 to 500, and particularly preferably 30 to 300.
  • the phenoxy resin (PR) preferably does not have an epoxy group at the end because a molded article having few gel defects can be easily obtained.
  • the polystyrene-equivalent Mn of the phenoxy resin (PR) is preferably 3,000 to 2,000,000, more preferably 5,000 to 100,000, and particularly preferably 10,000 to 50,000.
  • Mn is in such a range, a (meth)acrylic resin composition having high heat resistance and high strength can be obtained.
  • the glass transition temperature of the phenoxy resin (PR) is preferably 80°C or higher, more preferably 90°C or higher, and particularly preferably 95°C or higher. When the glass transition temperature of the phenoxy resin (PR) is too low, the heat resistance of the (meth)acrylic resin composition tends to be reduced.
  • the upper limit of the glass transition temperature is preferably 150°C. When the glass transition temperature of the phenoxy resin (PR) is too high, the resultant molded article tends to be brittle.
  • the phenoxy resin (PR) can be obtained, for example, by a condensation reaction of a divalent phenol compound and epihalohydrin or a polyaddition reaction of a divalent phenol compound and a bifunctional epoxy resin. This reaction can be performed in the absence of a solvent or in a solvent.
  • divalent phenol compound examples include: hydroquinone, resorcin, 4,4-dihydroxybiphenyl, 4,4'-dihydroxydiphenylketone, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 1,3-bis(
  • 4,4-dihydroxybiphenyl, 4,4'-dihydroxydiphenylketone, 2,2-bis(4-hydroxyphenyl)propane and 9,9'-bis(4-hydroxyphenyl)fluorene are preferred in view of physical properties and cost.
  • the bifunctional epoxy resin examples include an epoxy oligomer obtained by a condensation reaction of the aforementioned divalent phenol compound and epihalohydrin.
  • Specific examples of the bifunctional epoxy resin include: a hydroquinone diglycidyl ether, a resorcin diglycidyl ether, a bisphenol S type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a methyl hydroquinone diglycidyl ether, a chlorohydroquinone diglycidyl ether, a 4,4'-dihydroxydiphenyl oxide diglycidyl ether, a 2,6-dihydroxynaphthalene diglycidyl ether, a dichlorobisphenol A diglycidyl ether, a tetrabromobisphenol A type epoxy resin, and a 9,9'-bis(4-hydroxyphenyl) fluorene diglycidyl ether.
  • a bisphenol A type epoxy resin a bisphenol S type epoxy resin, a hydroquinone diglycidyl ether, a bisphenol F type epoxy resin, a tetrabromobisphenol A type epoxy resin, and a 9,9'-bis(4-hydroxyphenyl) fluorene diglycidyl ether are preferred in view of physical properties and cost.
  • Examples of a solvent used for manufacturing the phenoxy resin (PR) include aprotic organic solvents such as methyl ethyl ketone, dioxane, tetrahydrofuran, acetophenone, N-methyl pyrrolidone, dimethyl sulfoxide, N, N-dimethyl acetamide, and sulfolane.
  • aprotic organic solvents such as methyl ethyl ketone, dioxane, tetrahydrofuran, acetophenone, N-methyl pyrrolidone, dimethyl sulfoxide, N, N-dimethyl acetamide, and sulfolane.
  • Examples of a catalyst used for manufacturing the phenoxy resin (PR) include alkali metal hydroxide, a tertiary amine compound, a quaternary ammonium compound, a tertiary phosphine compound, and a quaternary phosphonium compound.
  • X in the formula (i) is preferably a divalent group derived from compounds expressed by the following formulas (j) to (1). Note that a position of two bonds composing a divalent group is not particularly limited if it is chemically acceptable.
  • X in the formula (i) is preferably a divalent group having two bonds which can be formed by extracting two hydrogen atoms from benzene rings in the compounds expressed by the formulas (j) to (1).
  • a divalent group having two bonds which can be formed by extracting one hydrogen atom from each of any two of the benzene rings in the compounds expressed by the formulas (k) to (1) is particularly preferred.
  • R 19 is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms, p is an integer of 1 to 4.
  • R 19 is a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or a cycloalkylidene group having 3 to 20 carbon atoms.
  • R 20 and R 21 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms.
  • n and m are each independently an integer of 1 to 4.
  • X may be a divalent group derived from a compound formed by condensing a plurality of benzene rings with an alicyclic or heterocyclic ring.
  • a divalent group derived from a compound having a fluorene structure or a carbazole structure may be used.
  • a structural unit expressed by the formula (i) is preferably a structural unit expressed by the following formulas (m) and (n), and is more preferably a structural unit expressed by the following formula (o).
  • a preferred form of the phenoxy resin (PR) preferably contains 10 to 1000 of such structural units.
  • R 22 is a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or a cycloalkylidene group having 3 to 20 carbon atoms.
  • R 23 is a linear or branched alkylene group having 1 to 6 carbon atoms.
  • Examples of a commercially-available phenoxy resin (PR) include YP-50 and YP-50S manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD., jER series manufactured by Mitsubishi Chemical Corporation, and PKFE and PKHJ manufactured by InChem.
  • the (meth)acrylic resin composition according to the present invention can contain other optional components as necessary.
  • other optional components include various additives such as a filler, an antioxidant, a thermal degradation inhibitor, an ultraviolet absorber, a light stabilizer, a lubricant, a mold release agent, a polymer processing aid, an antistatic agent, a flame retardant, a staining pigment, a light diffusing agent, an organic pigment, a delusterant, an impact resistance modifier, and a phosphor.
  • the total amount of these various additives is preferably 7 mass% or less, more preferably 5 mass% or less, and particularly preferably 4 mass% or less.
  • LA Ultraviolet light absorber
  • an ultraviolet light absorber (LA) having a molecular weight that is too small can cause foaming during molding of the (meth)acrylic resin composition.
  • the molecular weight of the ultraviolet light absorber (LA) is preferably greater than 200, more preferably 300 or more, particularly preferably 500 or more, and most preferably 600 or more.
  • the ultraviolet absorber (LA) is a compound that has the function of converting light energy into heat energy.
  • examples of the ultraviolet absorber (LA) include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic anilides, malonic acid esters, and formamidines. One or more types of them can be used.
  • benzotriazoles compounds having benzotriazole skeletons
  • triazines compounds having triazine skeletons
  • benzotriazoles examples include 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (trade name: TINUVIN329, manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (trade name: TINUVIN234, manufactured by BASF Corporation), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (LA-31, manufactured by ADEKA Corporation), and 2-(5-octylthio-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol.
  • triazines examples include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (LA-F70, manufactured by ADEKA Corporation), its analog hydroxyphenyl triazine ultraviolet absorber (CGL777, TINUVIN460, TINUVIN479, etc., manufactured by BASF Corporation), and 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine.
  • LA-F70 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine
  • CGL777, TINUVIN460, TINUVIN479, etc. manufactured by BASF Corporation
  • 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine examples include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-
  • UV absorber having the maximum value ⁇ max of the molar absorbance coefficient at a wavelength of 380 to 450 nm of equal to or less than 1,200 dm 3 ⁇ mol -1 cm -1 .
  • 2-ethyl-2'-ethoxy-oxalanilide trade name: Sanduvor VSU, manufactured by Clariant (Japan) K.K.
  • Clariant (Japan) K.K. and the like may be used.
  • the ultraviolet absorber examples include metal complexes having heterocyclic ligands which are disclosed in International Patent Publication Nos. WO2011/089794 and WO 2012/124395 , and Japanese Unexamined Patent Application Publication Nos. 2012-012476 , 2013-023461 , 2013-112790 , 2013-194037 , 2014-62228 , 2014-88542 , and 2014-88543 , etc.
  • metal complexes include a compound expressed by the following formula (p).
  • M is a metal atom.
  • Y 1 to Y 4 are each independently a divalent group other than a carbon atom (e.g., an oxygen atoms, a sulfur atoms, NH, and NR 28 ).
  • R 28 is a substituent of an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, an arallyl group or the like. The substituent may further have a substituent.
  • Z 1 and Z 2 are each independently a trivalent group (e.g., a nitrogen atom, CH, and CR 29 ).
  • R 29 is a substituent of an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, an arallyl group or the like.
  • the substituent may further have a substituent.
  • R 24 to R 27 are each independently a substituent of a hydrogen atom, an alkyl group, a hydroxyl group, a carboxyl group, an alkoxyl group, a halogeno group, an alkylsulfonyl group, a monophorinosulfonyl group, a piperidinosulfonyl group, a thiomorpholinosulfonyl group, and a piperazinosulfonyl group or the like.
  • the substituent may further have a substituent.
  • a to d each indicates values of R 21 to R 27 , respectively, each of which is independently an integer of 1 to 4.
  • heterocyclic ligand in the metal complex examples include 2,2'-iminobisbenzothiazole, 2-(2-benzothiazolylamino)benzoxazole, 2-(2-benzothiazolylamino)benzimidazole, (2-benzothiazolyl)(2-benzoimidazolyl)methane, bis(2-benzoxazolyl)methane, bis(2-benzothiazolyl)methane, bis[2-(N-substituted)benzoimidazolyl]methane, and derivatives of the above.
  • the central metal of the metal complex copper, nickel, cobalt, zinc and the like are preferred.
  • the metal complex is preferably dispersed in a medium such as a low molecular weight compound or a polymer for use.
  • the additive amount of the metal complex is preferably 0.01 to 5 parts by mass and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the (meth)acrylic resin composition according to the present invention. Since the metal complex has a large molar absorbance coefficient at a wavelength of 380 to 400nm, the amount to be added to obtain a desired sufficient ultraviolet absorbing effect can be reduced. Thus, degradation of the appearance of a molded article due to bleed-out or the like can be prevented. Further, since the metal complex has a high heat resistance, it is less subject to degradation or decomposition during molding. Further, since the metal complex has a high light resistance, it is possible to maintain the ultraviolet absorbing capability for a long time.
  • polymer particles non-crosslinked rubber particles having a particle diameter of 0.05 to 0.5 ⁇ m which can be manufactured by an emulsion polymerization method
  • the polymer particles may be single-layer particles composed of a polymer having a single composition and a single limiting viscosity, or may be a multilayer particles of two or more layers composed of two or more types of polymers having different compositions or limiting viscosities.
  • two-layer particles composed of an inner polymer layer having a low limiting viscosity and an outer polymer layer having a high limiting viscosity of 5 dl/g or more are preferred.
  • the polymeric processing aid (PA) preferably has a limiting viscosity of 3 to 6 dl/g. An improvement of moldability may be insufficient if the limiting viscosity is too low while moldability of the (meth)acrylic resin composition may be reduced if the limiting viscosity is too high. Specific examples of the polymeric processing aid include Metablen-P series manufactured by MITSUBISHI RAYON CO., LTD. and Paraloid series manufactured by The Dow Chemical Company. An amount of the polymer processing aid (PA) is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the (meth)acrylic resin (A) and the thermoplastic resin (B). Processing characteristics cannot be satisfactorily achieved if the blending amount is too small while the appearance of the molded article may be degraded if the blending amount is too large.
  • fillers examples include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate.
  • the amount of the filler in the (meth)acrylate resin composition according to the present invention is preferably 3 mass% or less and more preferably 1.5 mass% or less.
  • antioxidants include a phosphorus-based antioxidant, a hindered phenol-based antioxidant, and a thioether-based antioxidant.
  • One or more types of antioxidants can be used. Among them, use of a phosphorus-based antioxidant and a hindered phenol-based antioxidant is preferred, and a combined use of a phosphorus-based antioxidant and a hindered phenol-based antioxidant is more preferred in order to prevent degradation of optical properties due to coloring.
  • the mass ratio of the phosphorus-based antioxidant and the hindered phenol-based antioxidant is preferably 1:5 to 2:1 and more preferably 1:2 to 1:1.
  • Examples of the phosphorus-based antioxidant include 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite (trade name: ADK STAB HP-10, manufactured by ADEKA Corporation), tris(2,4-di-t-butylphenyl)phosphite (trade name: IRGAFOS168, manufactured by BASF Corporation), and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (trade name: ADK STAB PEP-36, manufactured by ADEKA Corporation).
  • hindered phenol-based antioxidant examples include pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF Corporation), and octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX1076, manufactured by BASF Corporation).
  • a thermal degradation inhibitor can prevent thermal degradation of a resin by trapping polymer radicals generated when exposed to high heat substantially in the absence of oxygen.
  • the thermal degradation inhibitor include 2-t-butyl-6-(3'-t-butyl-5'-methylhydroxybenzyl)-4-methylphenylacrylate (trade name: Sumilizer GM, manufactured by Sumitomo Chemical Co., Ltd.), 2,4-di-t-amyl-6-(3',5'-di-t-amyl-2'-hydroxy- ⁇ -methylbenzyl)phenylacrylate (trade name: Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.).
  • a light stabilizer is a compound that has the function of trapping radicals generated by oxidation with light.
  • Examples of the light stabilizer include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
  • a lubricant examples include stearic acid, behenic acid, stearamide acid, methylene bis-stearamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, hydrogenated oil.
  • Examples of a release agent include: higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as monoglyceride stearate and diglyceride stearate.
  • a higher alcohol and a glycerin fatty acid monoester are preferably used in combination.
  • the mass ratio of a higher alcohol and a glycerin fatty acid monoester is preferably 2.5/1 to 3.5/1 and more preferably 2.8/1 to 3.2/1.
  • an organic pigment a compound transforming ultraviolet light into visible light is preferably used.
  • Examples of a light diffusing agent and a delusterant include glass particles, polysiloxane crosslinked fine particles, crosslinked polymer particles, talc, calcium carbonate, and barium sulfate.
  • Examples of a phosphor include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent brightening agent, and a fluorescent bleach.
  • the raw film can be formed by a melt film-forming method or a solution film-forming method and is preferably formed by a melt film-forming method in view of productivity.
  • the melt film-forming method include an inflation method, a T-die method, a calender method and a cutting method, and the T-die method can be particularly, preferably adopted.
  • an extruder-type melt extrusion apparatus having a single or twin extrusion screws can be used.
  • a melt extrusion temperature is preferably 150 to 350°C, more preferably 200 to 300°C, and particularly preferably 230 to 270°C.
  • melt-kneading when melt-kneading is performed by using a melt-extrusion apparatus, it is preferred that the melt-kneading be performed, in order to prevent coloring, using a vent under reduced pressure or under a nitrogen stream. Further, it is preferred that a polymer filter be installed for manufacturing in order to remove foreign matters. Further, it is preferred that a gear pump be installed for manufacturing in order to achieve a high thickness accuracy.
  • a film obtained by the aforementioned manufacturing method is a raw film.
  • the raw film when the raw film satisfies physical properties according to the present invention without stretching, the raw film serves as an acrylic resin film.
  • An acrylic resin film may be obtained by satisfying physical properties according to the present invention using means other than stretching by heat treatment, energy ray irradiation and the like.
  • a process of manufacturing a raw film and a process of biaxially stretching the raw film may be conducted either continuously or discontinuously.
  • a thickness of a raw film is not limited to particular values, and is for example, preferably 10 to 500 ⁇ m.
  • a thickness distribution of the film is usually within ⁇ 10%, preferably within ⁇ 5%, more preferably within ⁇ 3% with respect to the average value.
  • the film having the thickness distribution of ⁇ 10% or greater is likely to have an uneven thickness because stress is concentrated on a part where the film thickness is small.
  • the raw film may contain other functional layers and the like as long as the effect according to the present invention is produced.
  • an adhesive layer a hard coat layer, an antireflective layer, an easily adhesive layer and the like may be contained.
  • the above-described raw film is used for the biaxially stretched film according to the present invention.
  • Stretching processing can increase heat resistance, mechanical strength and the like of the film.
  • a stretching method in the stretching process and for example, sequential biaxial stretching, simultaneous biaxial stretching, and tubular stretching may be used.
  • the stretching processing includes a preheating process, a stretching process and a heat-setting process, and relaxation process may be performed after the heat-setting process.
  • the stretching speed of each stretching direction may be the same as or different from each other, preferably 100 to 5,000%/min, more preferably 100 to 3,000%/min, and particularly preferably 500 to 1,000%/min.
  • the stretching speed is preferably 50 to 5,000%/min, and more preferably 100 to 3,000%/min.
  • a stretching temperature is, based on the glass transition temperature (Tc) of the thermoplastic resin composition (C) used in the present invention, preferably Tc to (T C +40°C), more preferably (T C +5°C) to (T C +35°C), even more preferably (T C +10°C) to (Tc+35°C), and particularly preferably (Tc+15°C) to (Tc+ 25°C).
  • Tc glass transition temperature
  • Tc glass transition temperature
  • a stretching magnification is preferably 1.01 to 12.25 times at an area magnification indicating an area ratio of the raw film to the stretched film, more preferably 1.10 to 9 times, even more preferably 2 to 6 times, and particularly preferably 3 to 5 times.
  • the area magnification is 1.01 times or less, toughness of the film may not increase, while when it is 12.25 times or more, mechanical strength of the film may be significantly reduced.
  • the heat-setting process is performed by keeping the film biaxially stretched as described above under the condition of a predetermined temperature range for a predetermined time within a fixed temperature range while both ends in at least one direction of the film are restrained, thereby achieving the effect of increasing heat resistance and mechanical strength of the film.
  • the temperatures used in the heat-setting process are, based on the glass transition temperature T C of the thermoplastic resin composition (C), a temperature of (T C -25°C) or higher but less than Tc, preferably a temperature of (T C -20°C) or higher but less than Tc, more preferably a temperature of (Tc-15°C) or higher but less than Tc, and particularly preferably a temperature of (T C -10°C) or higher but less than (Tc-2°C).
  • the heat-setting process performed in the temperature ranges can control the orientation state and the relaxation state of each component composing the resin composition (C), thereby obtaining a film having a high shrinkage starting temperature, a low linear expansion coefficient and impact resistance.
  • the content ratio of ingredients is set to be a low content ratio so that it can be effective, almost no blending effect is exhibited.
  • the content ratio of the thermoplastic resin (B) is set to be a low content ratio which is not expected to be generally effective.
  • the heat-setting temperature is lower than (T C -25°C)
  • the shrinkage starting temperature tends to be significantly reduced.
  • the heat-setting temperature is T C or higher, the linear expansion coefficient tends to increase.
  • the impact resistance may be reduced depending on the composition of the thermoplastic resin composition (C).
  • the aforementioned predetermined time varies with a raw film thickness, a stretching magnification, a stretching temperature, and a stretching speed of the thermoplastic resin composition (C), it is a time longer than the time during which stress of the film is reduced and becomes constant.
  • the measurement of the stress is preferably detected by a stress measuring apparatus installed in a jig for restraining the film.
  • the predetermined time may be determined based on the result of the stress detection during manufacturing, or may be set to a time determined based on the result of the stress detection in which a separate stretching test was performed in advance.
  • the (meth)acrylic resin (A) and the thermoplastic resin (B) are cooperatively molecularly orientated.
  • the heat -setting temperature is higher than Tc, both components cooperatively relax.
  • the heat-setting temperature is lower than (T C -25)°C, neither component sufficiently relaxes.
  • the heat-setting is performed at a temperature range of (T C -25)°C or higher but less than T C °C according to the present invention, only the (meth)acrylic resin (A) relaxes independently and the effect of increasing the shrinkage starting temperature is exhibited. Further, since the thermoplastic resin (B) is in a non-relaxed state, the effect of reducing the linear expansion coefficient is exhibited.
  • the relaxation process is a process of reducing a film width under a predetermined temperature environment while both ends in at least one direction of the film are restrained. It is preferred that the predetermined temperature environment is higher than the temperature in the heat-setting process and less than the glass transition temperature T B of the thermoplastic resin (B).
  • a longitudinal and/or horizontal relaxation processing may be applied simultaneously with or after the heat treatment.
  • the upper limit temperature in the relaxation process is the glass transition temperature T B of the thermoplastic resin (B).
  • a haze at a thickness of 100 ⁇ m is preferably 2.0% or less and more preferably 1.0% or less. This enhances transparency.
  • a tear strength of the film according to the present invention is preferably 1.5 gf (1.47 ⁇ 10- 2 N) or more, more preferably 1.6 gf (1.57 ⁇ 10- 2 N) or more, even more preferably 1.8 gf (1.77 ⁇ 10- 2 N) or more, and particularly preferably 2.0 gf (1.96 ⁇ 10- 2 N) or more,
  • the film according to the present invention can be used for a polarizer protective film, a decorative film and the like, and may contain an adhesive layer, a hard coat layer, an antireflection layer and the like.
  • the layer may be extended after being provided on the raw film, and may be provided on the stretched film by a method such as coating.
  • the evaluation items and the evaluation methods are as follows.
  • a resin to be measured was dissolved in 5 ml of tetrahydrofuran (THF), which was then passed through a filter having a pore size of 0.1 ⁇ m to obtain a sample solution.
  • THF tetrahydrofuran
  • HLC-8320 manufactured by Tosoh Corporation and provided with a differential refractive index detector (RI detector) was used.
  • RI detector differential refractive index detector
  • RI detector differential refractive index detector
  • Tetrahydrofuran (THF) was used as an eluant.
  • the temperature of a column oven was set at 40°C, 20 ⁇ l of the sample solution was introduced into the apparatus at an eluate flow rate of 0.35 ml/min, and the chromatogram was measured.
  • the chromatogram is a chart in which an electrical signal value (intensity Y) derived from a refractive index difference between the sample solution and a reference solution is plotted with respect to retention time X.
  • the GPC measurement was carried out with the use of 10 pieces of standard polystyrenes with a molecular weight in a range of 400 to 5,000,000, and a calibration curve indicating the relationship between the retention time and the molecular weight was created. On the basis of this calibration curve, Mw and Mw/Mn of the resin to be measured were determined. Note that the baseline of the chromatogram was served by a line connecting a point at which the slope of a peak on a higher molecular weight side in the GPC chart changed from zero to positive as viewed in a direction in which the retention time progressed and a point at which the slope of a peak on a lower molecular weight side changed from negative to zero as viewed in a direction in which the retention time progressed.
  • the baseline was served by a line connecting a point at which the slope of the peak on the highest molecular weight side changed from zero to positive and a point at which the slope of the peak on the lowest molecular weight side changed from negative to zero.
  • the 1 H-NMR measurement was performed on the resin to be measured.
  • a nuclear magnetic resonance apparatus ("ULTRA SHIELD 400 PLUS" manufactured by Bruker Corporation) was used as a measurement apparatus.
  • 10 mg of a sample 1 mL of deuterated chloroform was used as a deuterated solvent.
  • the measurement temperature was room temperature (20 to 25°C), and a total of 64 measurements were performed.
  • the glass transition temperature was measured in accordance with JIS K7121.
  • a DSC curve was measured under conditions that the temperature of the sample was once raised to 230°C, then cooled to the room temperature, and then again raised from the room temperature to 230°C at a temperature raising rate of 10°C /min using a differential scanning calorimetry equipment ("DSC-50" manufactured by Shimadzu Corporation).
  • a midpoint glass transition temperature obtained from the resultant DSC curve was set at the glass transition temperature.
  • a haze of the film was measured using a haze meter (HM-150 manufactured by Murakami Color Research Laboratory) in accordance with JIS K7136.
  • a total light transmittance of the film was measured using the haze meter (HM-150 manufactured by Murakami Color Research Laboratory) in accordance with JIS K7361-1.
  • a test piece of 4 mm (width) ⁇ 20 mm (length) ⁇ 40 ⁇ m (thickness) was cut out from the biaxially stretched film.
  • a thermomechanical analyzer TMA (“Q400EM” manufactured by TA Instruments) was used as a measurement device. The temperature of the test piece was raised from 25°C to 130°C at a temperature raising rate of 10°C/min under the condition of a distance between chucks of 8 mm and a load of 0.01 N to measure the amount of dimensional change thereof.
  • a linear thermal expansion coefficient was calculated from the slope of the amount of dimensional change in the temperature range of 50 to 90°C.
  • a test piece of 4 mm (width) ⁇ 20 mm (length) ⁇ 40 ⁇ m (thickness) was cut out from the biaxially stretched film.
  • a thermomechanical analyzer TMA (“Q400EM” manufactured by TA Instruments) was used as a measurement device. The temperature of the test piece was raised from 25°C to 130°C at a temperature raising rate of 10°C/min under the condition of a distance between chucks of 8 mm and a load of 0.01 N to measure the amount of dimensional change thereof.
  • the temperature at which the amount of film elongation becomes maximum was set at a shrinkage starting temperature.
  • a test piece of 25 mm (width) ⁇ 120 mm (length) was cut out from the biaxially stretched film with reference to JIS K7128-1 and a cut of 60 mm was made in the length direction thereof from the center point of a side in the width direction thereof.
  • AG-2000B manufactured by Shimadzu Corporation
  • a distance between the upper and lower sides of the chuck jig was set to 100 mm.
  • the side where the cut was made was fixed to the upper chuck jig, and the other side was fixed to the lower chuck jig.
  • a measured value obtained when tensile measurement was made under the condition of a tensile speed of 300 mm/min and a tensile distance of 100 mm was set to a tear strength.
  • a test piece of 80 mm ⁇ 80 mm ⁇ 40 ⁇ m (thickness) was cut out from the biaxially stretched film.
  • a film impact tester manufactured by YASUDA SEIKI SEISAKUSHO, LTD. was used to measure an impact resistance value when the test piece was broken by a sphere having a diameter of 12.7 ⁇ 0.2 mm ⁇ .
  • Acrylic coating liquid manufactured by Seiko advance Ltd., one-liquid evaporative drying type ink 2500 series, diluting solvent T-2500
  • the biaxially stretched film was dried at 80°C for 10 minutes using a hot-air generator to obtain a decorative film.
  • the resultant laminated molded article of 80 mm ⁇ 80 mm was used and set to have 1.5 J of an impact measurement capacity when a sphere having a diameter of 12.7 ⁇ 0.2 mm ⁇ was used. Then, an impact was applied to the test piece using a film impact tester (manufactured by Yasuda Seiki Co., Ltd.).
  • test piece similar to that used in the impact resistance test for the molded article was left under the high temperature environment of 105°C for 500 hours. The appearance of the test piece left for 500 hours was visually evaluated.
  • the raw material solution was poured into a tank reactor connected to the autoclave by a pipe up to 2/3 of the volume.
  • the polymerization reaction was started first by a batch method in a state in which the temperature was maintained at 140°C.
  • the polymerization conversion rate reached 55 mass%
  • the raw material solution was supplied from the autoclave to the tank reactor at a flow rate in which the average residence time becomes 150 minutes while maintaining the temperature at 140°C, and at the same time, the polymerization reaction of the batch method was switched to the polymerization reaction of the continuous flow type in which the reaction solution was extracted from the tank reactor at a flow rate corresponding to the supply flow rate of the raw material solution.
  • the polarization conversion rate in the steady state was 48 mass%.
  • the reaction liquid that was removed from the tank reactor which has been in the steady state was supplied to a multitubular heat exchanger having an inner temperature of 230°C at a flow rate in which the average residence time was two minutes and then heated. Then, the heated reaction liquid was introduced into a flash evaporator and volatile matter mainly composed of an unreacted monomer was removed to obtain a molten resin.
  • the molten resin from which the volatile matter was removed was supplied to a twin-screw extruder with the inner temperature of 260°C and discharged in a strand shape, then cut by a pelletizer to obtain a (meth)acrylic resin (A1-1) in the form of pellets.
  • the (meth)acrylic resin (A1-1) had a Mw of 112,000, a melt viscosity ⁇ of 1,000 Pa ⁇ s, an Mw/Mn of 1.86, a syndiotacticity (rr) of 52% and a glass transition temperature of 120°C, and the content of the MMA monomer unit was 100 mass% (polymethyl methacrylate (PMMA)).
  • the (meth)acrylic resin (B1-1 or A1-2) had a Mw of 70,000, a melt viscosity ⁇ of 1,200 Pa ⁇ s, an Mw/Mn of 1.06, a syndiotacticity (rr) of 75% and a glass transition temperature of 132°C, and the content of the MMA monomer unit was 100 mass% (polymethyl methacrylate (PMMA)).
  • PA polymer processing aids
  • thermoplastic resin composition (C1) 90 parts by mass of a (meth)acrylic resin (A1-1), 10 parts by mass of a (meth)acrylic resin (B2-1) and 2 parts by mass of a polymer processing aid (PA-1) were mixed, and using an twin-screw extruder ("KZW20TW-45MG-NH-600" manufactured by TECHNOVEL CORPORATION), the resultant mixture was melt-kneaded at 250°C and the resultant melt-kneaded matter was extruded, whereby a thermoplastic resin composition (C1) was manufactured. Physical properties of the thermoplastic resin composition (C1) were evaluated. Table 1 shows the compositions of the thermoplastic resin composition (C1) and the results of the evaluation.
  • thermoplastic resin composition (C1) was dried at 80°C for 12 hours. Using a 20 mm ⁇ single-screw extruder (manufactured by OCS GmbH), at a resin temperature of 260°C, the thermoplastic resin composition (C1) was extruded from a T-die and taken up by a roll having a surface temperature of 100°C to obtain a raw film having a width of 120 mm and a thickness of 160 ⁇ m. Table 1 shows the results of the evaluation.
  • a part of the resultant film having a size of 100 mmm ⁇ 100 mm was cut out therefrom.
  • Biaxial stretching was performed on this film using a two-tank batch biaxial stretching tester. In a first tank, simultaneous biaxial stretching was performed on the film under the conditions of a stretching temperature of 135°C, a stretching speed of 860%/min, and a stretching magnification of 2 ⁇ 2, and in a second tank, subsequently, heat-setting was performed on the film at a heat-setting temperature of 115°C for 90 seconds, and then the film was rapidly cooled to obtain a stretched film (F1) having a thickness of 40 ⁇ m.
  • Table 1 shows the stretching conditions and the results of the evaluation of the biaxially stretched film.
  • Examples 2 to 9 were each evaluated by obtaining thermoplastic resin compositions (C2) to (C9) and biaxially stretched films (F2) to (F9) in the same manner as that in Example 1 except that the compositions and stretching conditions were changed.
  • Table 1 shows the compositions, the stretching conditions and the results of the evaluation. Note that in Example 3, a mixture composed of 78 parts by mass of A1-1 and 19.5 parts by mass of A1-2 (equivalent to B1-1) is regarded as a (meth)acrylic resin (A1). The glass transition temperature of this mixture was 122°C.
  • Comparative Examples 1 to 10 were each evaluated by obtaining thermoplastic resin compositions (C1), (C5), (C8), (C10) and (C11) and biaxially stretched films (F10) to (F19) in the same manner as that in Example 1 except that the compositions and stretching conditions were changed.
  • Table 2 shows the compositions, the stretching conditions and the results of the evaluation.
  • thermoplastic resin composition (C12) 42 parts by mass of a (meth)acrylic resin (A1-1), 58 parts by mass of a (meth)acrylic resin (B1-1) and 2 parts by mass of a polymer processing aid (PA-2) were mixed, and using an twin-screw extruder ("KZW20TW-45MG-NH-600" manufactured by TECHNOVEL CORPORATION), the resultant mixture was melt-kneaded at 250°C and the resultant melt-kneaded matter was extruded, whereby a thermoplastic resin composition (C12) was manufactured. Physical properties of the thermoplastic resin composition (C12) were evaluated. Table 2 shows the compositions of the thermoplastic resin composition (C12) and the results of the evaluation.
  • thermoplastic resin composition (C12) was dried at 80°C for 12 hours and then supplied to a 20 mm ⁇ single-screw extruder (manufactured by OCS GmbH).
  • the thermoplastic resin composition was melt-kneaded at a cylinder temperature of 260°C, and then extruded from a T-die and taken up by a roll having a surface temperature of 100°C to obtain a raw film having a width of 500 mm and a thickness of 160 ⁇ m.
  • Table 2 shows the results of the evaluation.
  • thermoplastic resin composition (C4) was manufactured. Physical properties of the thermoplastic resin composition (C4) were evaluated. Table 2 shows the compositions of the thermoplastic resin composition (C4) and the results of the evaluation.
  • thermoplastic resin composition (C4) was dried at 80°C for 12 hours and then supplied to a 20 mm ⁇ single-screw extruder (manufactured by OCS GmbH).
  • the thermoplastic resin composition was melt-kneaded at a cylinder temperature of 260°C, and then extruded from a T-die and taken up by a roll having a surface temperature of 100°C to obtain a raw film having a width of 500 mm and a thickness of 160 ⁇ m.
  • Table 2 shows the results of the evaluation.
  • the resultant raw film was successively supplied to a tenter-type simultaneous biaxial stretching machine at a conveyance speed of 2 m/min.
  • This biaxial stretching machine executes the following processes (I) to (V) in an air circulation type drying oven.
  • Each of the tenter clamps includes a pantograph that can extract and retract and runs along one of the end parts of the film in the width direction and a plurality of clips that are provided in the pantograph and hold one of the end parts of the film.
  • the film was relaxed both in the longitudinal direction and the width direction with the relaxation rate of 5% while heating the film to 135°C in such a way that the stretching magnification in the longitudinal direction after the relaxation becomes twice and the stretching magnification in the width direction after the relaxation becomes twice (process (IV)).
  • the relaxation speed in the longitudinal direction and the relaxation speed in the width direction were both 80%/min.
  • both of the end parts of the film held by the pair of tenter clamps were released while conveying the film at a conveyance speed of 4 m/min.
  • the film was wound on a resin core in a roll shape at a winding-up tension of 90 N/m (process (VII)) to obtain a stretched film (F20).
  • Table 2 shows the results of the evaluation.
  • thermoplastic resin compositions (C1) to (C9) containing the (meth)acrylic resins (A) having a glass transition temperature T A of 140°C or lower and the thermoplastic resins (B) having a glass transition temperature of (T A +10°C) or higher were manufactured.
  • the thermoplastic resin compositions (C1) to (C9) were formed into a film to obtain a raw film and stretched films (F1) to (F9) were manufactured through the stretching process and the heat-setting process.
  • Each of the stretched films (F1) to (F9) obtained in Examples 1 to 9 had high transparency, a linear expansion coefficient of 60 ppm or less, a high heat resistance of which a shrinkage starting temperature was 110°C or higher, and an excellent impact resistance of which an impact resistance strength was 4.5 J/mm or more.
  • Comparative Example 1 using a thermoplastic resin composition (C10) composed of the (meth)acrylic resin (A1-1) and the polymer processing aid (PR-1), the resultant stretched film (F10) had a high linear expansion coefficient exceeding 60 ppm/°C.
  • a shrinkage starting temperature and/or a linear expansion coefficient of the stretched films (F11) and (F12), which were obtained after the stretching process and the heat-setting process using the raw film obtained from the thermoplastic resin composition (C10) was/were insufficient.
  • the heat resistance under high temperature and high humidity environment was insufficient.
  • the impact resistance strength was insufficient.
  • the stretched film (F18) obtained after the stretching process and the heat-setting process using the raw film obtained from the thermoplastic resin composition (C8) had a low shrinkage starting temperature.
  • the stretched films (F19) and (F20) obtained after the stretching process and the heat-setting process using the raw film obtained from the thermoplastic resin composition (C8) or (C12) had a high linear expansion coefficient and a low impact resistance strength.
  • the impact resistance strength was insufficient.
  • stretching processing was not performed and thus the impact resistance was significantly low.
  • the films obtained in Examples have a high light transmittance, a low haze, a low linear expansion coefficient, a high shrinkage starting temperature, and an excellent impact resistance as compared with the films obtained in Comparative Examples.
  • a film having a high light transmittance and a low haze is suitable for use as optical members.
  • a winding state of a film having a low linear expansion coefficient is unlikely to change when it is used as a roll during actual use, and thus the film quality is maintained and the possibility of occurrence of warpage is reduced when it is laminated with a low linear expansion material. Accordingly, a quality of a molded article is stable.
  • a film having a high shrinkage starting temperature can be used for a molded article under a harsh environment, for example, a higher temperature environment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polarising Elements (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
EP18751700.8A 2017-02-07 2018-02-05 Acrylic resin biaxially stretched film and method for manufacturing the same Active EP3581609B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017020052 2017-02-07
PCT/JP2018/003847 WO2018147234A1 (ja) 2017-02-07 2018-02-05 アクリル系樹脂二軸延伸フィルムおよびその製造方法

Publications (3)

Publication Number Publication Date
EP3581609A1 EP3581609A1 (en) 2019-12-18
EP3581609A4 EP3581609A4 (en) 2020-11-25
EP3581609B1 true EP3581609B1 (en) 2023-08-02

Family

ID=63108209

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18751700.8A Active EP3581609B1 (en) 2017-02-07 2018-02-05 Acrylic resin biaxially stretched film and method for manufacturing the same

Country Status (6)

Country Link
EP (1) EP3581609B1 (ko)
JP (1) JP7055108B2 (ko)
KR (1) KR102478708B1 (ko)
CN (1) CN110352212B (ko)
TW (1) TWI767987B (ko)
WO (1) WO2018147234A1 (ko)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020164680A (ja) * 2019-03-29 2020-10-08 株式会社クラレ （メタ）アクリル系樹脂フィルム
WO2021020426A1 (ja) * 2019-07-30 2021-02-04 株式会社クラレ メタクリル樹脂組成物、樹脂改質剤、成形体およびフィルムならびにフィルムの製造方法
KR102593637B1 (ko) * 2020-02-17 2023-10-24 삼성에스디아이 주식회사 편광자, 편광판 및 이를 포함하는 광학표시장치

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0243023A (ja) * 1988-08-04 1990-02-13 Kyowa Gas Chem Ind Co Ltd 加熱形状安定性の優れたフィルムまたはシートおよびそれらの製造法
JPH0335432A (ja) 1989-06-30 1991-02-15 Nippon Columbia Co Ltd フォーカスサーボ回路
US5264527A (en) 1989-07-10 1993-11-23 Elf Atochem S.A. Acrylic triblock copolymers, their preparation and their application to the manufacture of elastomeric articles
JP3334177B2 (ja) 1992-09-09 2002-10-15 三菱化学株式会社 メタクリル系ブロック共重合体およびその製造方法
DE602006020861D1 (de) * 2005-05-11 2011-05-05 Mitsubishi Plastics Inc Wärmeschrumpffolie, unter verwendung der folie hergestellte formkörper und wärmeschrumpfetiketten und unter verwendung der formkörper hergestellte oder mit den etiketten versehene behälter
US20060272766A1 (en) * 2005-06-03 2006-12-07 Hebrink Timothy J Optical bodies and method of making optical bodies including acrylate blend layers
JP2008101202A (ja) * 2006-09-21 2008-05-01 Toray Ind Inc アクリル系フィルム
JP2008231234A (ja) * 2007-03-20 2008-10-02 Toray Ind Inc 熱可塑性樹脂フィルム
KR101065198B1 (ko) * 2007-09-17 2011-09-19 주식회사 엘지화학 광학필름 및 이의 제조방법
JP5215771B2 (ja) * 2008-08-08 2013-06-19 株式会社日本触媒 フィルム及びその製法
JP5154344B2 (ja) * 2008-08-29 2013-02-27 株式会社日本触媒 延伸フィルムの製造方法
JP2010243818A (ja) * 2009-04-07 2010-10-28 Sekisui Chem Co Ltd 位相差補償フィルムの製造方法、位相差補償フィルム、複合偏光板、偏光板及び液晶表示装置
CA2786425C (en) 2010-01-19 2016-12-20 Sumitomo Seika Chemicals Co., Ltd. Composition for ultraviolet absorbent substance and ultraviolet absorbent substance comprising same
JP5400717B2 (ja) 2010-06-30 2014-01-29 住友精化株式会社 合成樹脂用安定化剤、該安定化剤を含有する合成樹脂組成物および樹脂部材
JP5897249B2 (ja) 2010-08-31 2016-03-30 住友化学株式会社 樹脂組成物の製造方法
JP2012096461A (ja) * 2010-11-02 2012-05-24 Nippon Shokubai Co Ltd 光学フィルムの製造方法
KR101295306B1 (ko) * 2010-11-23 2013-08-12 엘지엠엠에이 주식회사 메타크릴계 공중합체 및 이를 포함하는 위상차 필름
JP2014101394A (ja) 2011-03-11 2014-06-05 Sumitomo Seika Chem Co Ltd 紫外線吸収部材用組成物およびこれを用いた紫外線吸収部材
JP2013023461A (ja) 2011-07-20 2013-02-04 Sumitomo Seika Chem Co Ltd 金属錯体、これを含有する紫外線吸収部材用組成物およびこれを用いた紫外線吸収部材
JP2013112790A (ja) 2011-11-30 2013-06-10 Sumitomo Seika Chem Co Ltd 高分子錯体、重合性組成物、およびそれらを含有する紫外線吸収部材
JP2013194037A (ja) 2012-03-22 2013-09-30 Sumitomo Seika Chem Co Ltd 銅錯体、これを含有する紫外線吸収部材用組成物およびこれを用いた紫外線吸収部材
WO2014021264A1 (ja) 2012-07-30 2014-02-06 電気化学工業株式会社 メタクリル樹脂耐熱性向上用の共重合体
JP2014062228A (ja) 2012-08-31 2014-04-10 Sumitomo Seika Chem Co Ltd 紫外線吸収部材用組成物およびこれを用いた紫外線吸収部材
JP2014064519A (ja) 2012-09-26 2014-04-17 Yanmar Co Ltd コンバイン
JP2014088542A (ja) 2012-10-05 2014-05-15 Sumitomo Seika Chem Co Ltd 紫外線吸収部材用組成物およびこれを用いた紫外線吸収部材
JP2014088543A (ja) 2012-10-05 2014-05-15 Sumitomo Seika Chem Co Ltd 紫外線吸収部材用組成物およびこれを用いた紫外線吸収部材
KR101914815B1 (ko) * 2013-09-30 2018-11-05 주식회사 엘지화학 광학 필름용 수지 조성물, 이를 이용하여 형성된 광학 필름, 이를 포함하는 편광판 및 화상 표시 장치
CN106163764B (zh) * 2014-03-31 2018-11-27 株式会社可乐丽 双轴拉伸薄膜及其制造方法、偏振器保护膜、装饰薄膜和层叠薄膜
JP6407270B2 (ja) * 2014-05-30 2018-10-17 株式会社クラレ メタクリル樹脂組成物
EP3219753B1 (en) * 2014-11-14 2020-04-01 Kuraray Co., Ltd. Methacrylic resin composition and molded body
KR102381502B1 (ko) * 2014-11-19 2022-03-31 주식회사 쿠라레 아크릴계 필름
JP6424084B2 (ja) * 2014-12-17 2018-11-14 株式会社クラレ フィルム及びフィルムの製造方法

Also Published As

Publication number Publication date
TWI767987B (zh) 2022-06-21
EP3581609A1 (en) 2019-12-18
TW201835204A (zh) 2018-10-01
CN110352212A (zh) 2019-10-18
KR102478708B1 (ko) 2022-12-16
CN110352212B (zh) 2022-04-01
EP3581609A4 (en) 2020-11-25
WO2018147234A1 (ja) 2018-08-16
KR20190112123A (ko) 2019-10-02
JP7055108B2 (ja) 2022-04-15
JPWO2018147234A1 (ja) 2019-11-21

Similar Documents

Publication Publication Date Title
EP3438142B1 (en) Methacrylic resin composition and molded body
EP2998328B1 (en) Film
KR102394025B1 (ko) 메타크릴 수지 또는 메타크릴 수지 조성물
JP6258307B2 (ja) メタクリル樹脂組成物およびその成形体
JP6328499B2 (ja) メタクリル系樹脂組成物、成形体、樹脂フィルム、偏光子保護フィルム、および位相差フィルム
KR20170088826A (ko) 아크릴계 필름
JP7045994B2 (ja) メタクリル樹脂組成物とその製造方法、成形体、フィルム、積層フィルム、積層成形体
EP3219753B1 (en) Methacrylic resin composition and molded body
EP3581609B1 (en) Acrylic resin biaxially stretched film and method for manufacturing the same
JP6827272B2 (ja) 変性メタクリル樹脂および成形体
JP7352575B2 (ja) メタクリル樹脂組成物、フィルムおよび積層体
EP2868673A1 (en) Method for producing (meth)acrylic resin composition
CN108973281B (zh) 树脂层叠体
CN108928075B (zh) 曲面状树脂层叠体
EP3095800B1 (en) Copolymer, and molded article
JP2020164680A (ja) （メタ）アクリル系樹脂フィルム
EP4317209A1 (en) Methacrylic copolymer, methacrylic resin composition and method for producing same, and molded body
WO2020100913A1 (ja) 変性メタクリル樹脂および成形体
JP6649177B2 (ja) メタクリル酸エステル共重合体および成形体
EP4130058A1 (en) Methacrylic copolymer, composition, shaped object, method for producing film or sheet, and layered product

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190905

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20201028

RIC1 Information provided on ipc code assigned before grant

Ipc: C08L 33/12 20060101ALI20201022BHEP

Ipc: B29C 55/16 20060101ALI20201022BHEP

Ipc: C08J 5/18 20060101AFI20201022BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230223

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230517

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018054548

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20230802

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1594709

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231204

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231102

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231202

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231103

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231212

Year of fee payment: 7

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018054548

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230802

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT